Reactive liquid crystal compounds

Abstract: The invention relates to reactive liquid crystal compounds of formula I R¹-P-X-(A¹-Z¹) n -A²-R² I wherein R¹ is CH₂ = CW-COO-, CH₂ = CH-, HWN-, HS-CH₂-(CH₂)m-COO- with W being H, Cl or alkyl with 1-5 C atoms and m being 1-7, P is alkylene with up to 12 C atoms, it being also possible for one or more CH₂ groups to be replaced by O in such a manner that oxygen atoms are not directly linked to one another, X is -O-, -S-, -COO-, -OCO- or a single bond, R² is alkyl radical with up to 15 C atoms which is unsubstituted, mono-or polysubstituted by halogen, it being also possible for one or more CH₂ groups in these radicals to be replaced, in each case independently of one another, by -O-, -S-, -CO-, -OCO-, -CO-O- or -O-CO-O- in such a manner that oxygen atoms are not directly linked to one another, or alternatively R² has one of the meaning given for R¹-P-X or is CN, F, Cl or -V-Q-T wherein V is -O-, -S- or a single bond, Q is -CH₂-, -CHF-, -CF₂-, and T is F or Cl, n is 1 or 2, A¹, A₂ are independently from each other 1,4-phenylene which is unsubstituted or mono- or polysubstituted by F, Cl, CN or -W-C r H s F 2r+l-s , and one of A¹ and A² may also denote pyridine-2,5-diyl or pyrimidine-2,5-diyl, Z¹ is independently from each other -CO-O-, -O-CO-, -CH₂CH₂- or a single bond, in case n = 2 both the moieties A¹ as well as both the moieties Z¹ are having the meaning given above, independently from each other r is 1 or 2, s is 0, 1, 2, 3, 4 or 5, W is a single bond, -O-, -S- or -CO-, with the provisos (i) that at least one of A¹ and A² is 1,4-phenylene which is mono-or polysubstituted by Cl, CN or -W-C r H s F 2r+l-s , it also being possible for this substituted 1,4-phenylene group to be additionally substituted by one or more F-atoms, and (ii) that in case n = 2 (a) only one of Z¹ is -COO-or -OCO- or (b) at least one of A¹ and A² is double substituted or (c) at least two of A¹ and A² are substituted.

Description: The invention relates to reactive liquid crystal compounds of formula I R 1 -P-X-(A 1 -Z 1 ) n -A 2 -R 2 wherein R 1 is CH 2 = CW 1 -COO-, CH 2 = CH-, HW 1 N-, HS-CH 2 -(CH 2 )m-COO- with W 1 being H, Cl or alkyl with 1-5 C atoms and m being 1-7, P is alkylene with up to 12 C atoms, it being also possible for one or more CH 2 groups to be replaced by O, X is -O-, -S-, -COO-, -OCO- or a single bond, R 2 is alkyl radical with up to 15 C atoms which is unsubstituted, mono- or polysubstituted by halogen, it being also possible for one or more CH 2 groups in these radicals to be replaced, in each case independently of one another, by -O-, -S-, -CO-, -O-CO-, -CO-O- or -O-CO-O- in such a manner that oxygen atoms are not directly linked to one another, or alternatively R 2 has one of the meaning given for R 1 -P-X or is CN, F, Cl or -V-Q-T wherein V is -O-, -S- or a single bond, Q is -CH 2 -, -CHF-, -CF 2 -, and T is F or Cl, n is 1 or 2, A 1 , A 2 are independently from each other 1,4-phenylene which is unsubstituted or mono- or polysubstituted by F, Cl, CN or -W 2 -C r H s F 2r+1-s , and one of A 1 and A 2 may also denote pyridine-2,5-diyl or pyrimidine-2,5-diyl, Z 1 is independently from each other -CH 2 -CH 2 - or a single bond, in case n=2 both the moieties A 1 as well as both the moieties Z 1 are having the meaning given above, independently from each other, r is 1 or 2, s is 0, 1, 2, 3, 4 or 5, W 2 is a single bond, -O-, -S- or -CO-, with the provisos (i) that at least one of A 1 and A 2 is 1,4-phenylene which is mono- or polysubstituted by Cl, CN or -W 2 -C r H s F 2r+1-s , it also being possible for this substituted 1,4-phenylene group to be additionally substituted by one or more F-atoms, and (ii) that in case n=2 at least one of A 1 and A 2 is double substituted or at least two of A 1 and A 2 are substituted, characterized in that said compound is laterally di- or higher substituted by CN or -W 2 -C r H s F 2r+1-s , reactive liquid crystal compounds of formula I2 R 1 -P-X-A 1 -Z 1 -A 2 -R 2 wherein R 1 is CH 2 =CW 1 -COO-, CH 2 =CH-, HW 1 N- or HS-CH 2 -(CH 2 ) m -COO-, with W being H, Cl or alkyl with 1-5 C-atoms and m being 1-7, P is alkylene with up to 12 C atoms, it being also possible for one or more CH 2 groups to be replaced by O in such a manner that oxygen atoms are not directly linked to one another, X is -O-, -S-, -COO-, -OCO- or a single bond, R 2 is an alkyl radical with up to 15 C atoms which is unsubstituted, mono- or polysubstituted by halogen, it being also possible for one or more CH 2 groups in these radicals to be replaced, in each case independently of one another, by -O-, -S-, -CO-, -O-CO-, -CO-O- or -O-CO-O- in such a manner that oxygen atoms are not linked directly to one another, or alternatively R 2 has one of the meanings given for R 1 -P-X or is CN, F, Cl or -V-Q-T wherein V is-O-, -S- or a single bond, Q is -CH 2 -, -CHF-, -CF 2 -, and T is F or Cl, A 1 , A 2 are independently from each other 1,4-phenylene which is unsubstituted or mono- or polysubstituted by F, Cl, CN or -W 2 -C r H s F 2r+1-s , and one of A 1 and A 2 may also denote pyridine-2,5-diyl or pyrimidine-2,5-diyl, Z 1 is independently from each other -CH 2 -CH 2 - or a single bond, r is 1 or 2, s is 0, 1, 2, 3, 4 or 5, W 2 is a single bond, -O-, -S- or -CO-, with the proviso that at least one of A 1 and A 2 is 1,4-phenylene which is monosubstituted by Cl, CN or -W 2 -C r H s F 2r+1-s , it also being possible for this substituted 1,4-phenylene group to be additionally substituted by one or more F-atoms, characterized in that said compound is laterally monosubstituted by -Cl, -CN or -W 2 -C r H s F 2r+1-s , reactive liquid crystal compounds of formula I3 R 1 -P-X-A 1 -Z 1 -A 1 -Z 1 -A 2 -R 2 wherein R 1 is CH 2 =CW 1 -COO-, CH 2 =CH-, HW 1 N- or HS-CH 2 -(CH 2 ) m -COO-, with W 1 being H, Cl or alkyl with 1-5 C-atoms and m being 1-7, P is alkylene with up to 12 C atoms, it being also possible for one or more CH 2 groups to be replaced by O in such a manner that oxygen atoms are not directly linked to one another, X is -O-, -S-, -COO-, -OCO- or a single bond, R 2 is an alkyl radical with up to 15 C atoms which is unsubstituted, mono- or polysubstituted by halogen, it being also possible for one or more CH 2 groups in these radicals to be replaced, in each case independently of one another, by -O-, -S-, -CO-, -O-CO-, -CO-O- or -O-CO-O- in such a manner that oxygen atoms are not linked directly to one another, or alternatively R 2 has one of the meanings given for R 1 -P-X or is CN, F, Cl or -V-Q-T wherein V is-O-, -S- or a single bond, Q is -CH 2 -, -CHF-, -CF 2 -, and T is F or Cl, A 1 , A 2 are independently from each other 1,4-phenylene which is unsubstituted or mono- or polysubstituted by F, Cl, CN or -W 2 -C r H s F 2r+1-s , and one of A 1 and A 2 may also denote pyridine-2,5-diyl or pyrimidine-2,5-diyl, Z 1 is independently from each other -CH 2 -CH 2 - or a single bond, in case n=2 both the moieties A 1 as well as both the moieties Z 1 are having the meaning given above, independently from each other, r is 1 or 2, s is 0, 1, 2, 3, 4 or 5, W 2 is a single bond, -O-, -S- or -CO-, with the proviso that at least one of A 1 and A 2 is 1,4-phenylene which is mono- or polysubstituted by Cl, CN or -W 2 -C r H s F 2r+1-s , it also being possible for this substituted 1,4-phenylene group to be additionally substituted by one or more F-atoms, characterized in that said compound is laterally monosubstituted by -Cl, -CN or -W 2 -C r H s F 2r+1-s ., with the proviso that compounds being only monosubstituted by Cl are excluded. The invention furthermore relates to the preparation of such compounds and to their use in electrooptical scattering systems and for the preparation of oriented liquid crystal polymers. Reactive liquid crystal compounds can be polymerized in situ, whilst in their liquid crystal phase, to give highly crosslinked anisotropic films which can be used, for example, as polarizing beam splitters (see, for example, EP 0,428,213). Reactive liquid crystal compounds have furthermore been proposed for electrooptical scattering systems (see, for example, EP 0,451,905). Reactive liquid crystal diesters of formula which are laterally substituted by a methyl group are mentioned in EP 0,331,233. These reactive liquid crystalline compounds often exhibit, however, rather high melting points and disadvantageous values of the birefringence. Furthermore, reactive liquid crystals, polymers obtained thereof and their uses are disclosed in the prior art documents EP 0 501 563 A1, EP 0 484 972 A2, WO 93/22397 Al, WO 94/08268 A1 and by K. Geibel et al., Advanced Materials 5 , 2 (1993), p. 107-109. In view of the broad range of applications of reactive liquid crystal compounds it was desirable to have available further compounds of this type which fulfill the various requirements such as a reasonably low melting point, a high birefringence, a broad mesogenic range and preferably an enantiotropic nematic range to a high degree. It was an object of the present invention to provide new reactive liquid crystalline compounds with advantageous properties thus extending the pool of reactive liquid crystal compounds available to the expert. Other objects of the present invention can be taken from the following detailed specification. The present invention thus relates to reactive liquid crystal compounds of formula I and to their use in electrooptical systems of scattering type and for the preparation of oriented liquid crystal polymers. The invention furthermore relates to the preparation of compounds according to formula I. Above and below, the term reactive liquid crystalline compounds refers to reactive rod-like molecules of formula I or other rod-like reactive compounds which may be enantiotropic, monotropic or isotropic, preferably, however, enentiotropic or monotropic. In the compounds of formula I, A 1 and A 2 can be independently from each other an unsubstituted or a substituted 1,4-phenylene group of formula X 2 , X 3 , X 5 and X 6 can be independently from each other H, F, Cl, CN or -W 2 -C r H s F 2r+1-s . In the following, for the sake of simplicity, the following notation will be used: Phe. 2 X 2 3 X 3 5 X 5 6 X 6 is a 1,4-phenylene group carrying in 2-position the group X 2 , in 3-position the group X 3 etc.; in case X 2 , X 3 , X 5 and/or X 6 , denote H, this will not be specified in above notation, i.e. only true substitutions will be listed. Thus Phe, for example, is an unsubstituted 1,4-phenylene group while Phe.2F 5 Cl is a 2-fluoro-5-chloro-1,4-phenylene group. Furthermore, Pyr is pyrimidine-2,5-diyl, Pyd is pyridine -2,5-diyl and Nap is a naphthalene-2,6-diyl group. The notation Pyr and Pyd in each case include the 2 possible positional isomers. The compounds according to formula I comprise 2- and 3-ring compounds (n = 1 or 2) of formula I2 and I3: R 1 -P-X-A 1 -Z 1 -A 2 -R 2 R 1 -P-X-A 1 -Z 1 -A 1 -Z 1 -A 2 -R 2 In the 3-ring compounds of formula 13, the ring groups A 1 can be chosen independently from each other. Compounds according to formula I which are laterally monofluorinated often exhibit smectic phases ... and are not covered by the present invention. Contrary to this, compounds according to formula I which are laterally monosubstituted by -Cl, -CN or -W 2 -C r H 2r+1-s and, in particular, by -Cl,-CH 3 , -O-CH 3 , -CF 3 , -OCF 3 , -CH 2 F, -OCH 2 F, -CHF 2 , -OCHF 2 , -C 2 H 5 , -S-CH 3 , -S-CF 3 are characterized by advantageous properties and the tendency to form smectic phases is considerably reduced. Compounds according to formula I which are laterally di- or higher substituted by -F, -Cl, -CN and/or -W 2 -C r H 2r+1-s and, in particular, by -F, -Cl, -CN, -CH 3 , -OCH 3 , -CF 3 and/or -OCF 3 are furthermore preferred. This substitution pattern distinctly supresses smectic phases and promotes formation of the nematic phase. 3-ring compounds according to formula I wherein both bridging groups Z 1 are -COO- and/or -OCO- are often characterized by an insufficient stability and these compounds are not covered by the present invention. Especially preferred is a smaller group of 2-ring compounds exhibiting the following structures for -A 1 -Z 1 -A 2 -; -Phe.2CH 3 -Phe- -Phe.3CH 3 -Phe- -Phe.2Cl-Phe- -Phe.3Cl-Phe- -Phe.2CN-Phe- -Phe.3CN-Phe- -Phe.2Cl3F-Phe- -Phe.2OCH3-Phe- -Phe.3OCH3-Phe- -Phe.2C 2 H 5 -Phe- -Phe.3C 2 H 5 -Phe- -Phe.2CF 3 -Phe- -Phe.3CF 3 -Phe- -Phe.2CH 3 -Phe.2CH 3 - -Phe.2CH 3 -Phe.3CH 3 - -Phe.2CH 3 -Phe.2F- -Phe.2CH 3 -Phe.3F- -Phe.2CH 3 -Nap- -Phe.2Cl-Nap- -Phe.3CH 3 -Nap- -Phe.3Cl-Nap- -Phe.2CH 3 -Pyr- -Phe.2Cl-Pyr- -Phe.2CH 3 -Pyd- -Phe.2Cl-Pyd- -Phe.2CH 3 -CH 2 CH 2 -Phe- -Phe.3CH 3 -CH 2 CH 2 -Phe- -Phe.2Cl-CH 2 CH 2 -Phe- -Phe.3Cl-CH 2 CH 2 -Phe- -Phe.2CN-CH 2 CH 2 -Phe- -Phe.3CN-CH 2 CH 2 -Phe- -Phe.2Cl3F-CH 2 CH 2 -Phe- -Phe.2OCH 3 -CH 2 CH 2 -Phe- -Phe.2OCF 3 -CH 2 CH 2 -Phe- -Phe.3OCH 3 -CH 2 CH 2 -Phe- -Phe.2C 2 H 5 -CH 2 CH 2 -Phe- -Phe.2C 2 H 5 -CH 2 CH 2 -Phe- -Phe.2CF 3 -CH 2 CH 2 -Phe- -Phe.3CF 3 -CH 2 CH 2 -Phe- The 3-ring compounds according to formula 13 preferably exhibit the following structures for -A 1 -Z 1 -A 1 -Z 1 -A 2 : In these structures I3-a, I3-b and I3-c, L 1 and L 2 denote independently from each other -Cl, -F, -CN and W 2 -C r H 2r+1-s and, in particular, -Cl, -F, -CN, -CH 3 , -OCH 3 , -CH 2 F, -OCH 2 F, -CHF 2 , -OCHF 2 , -CF 3 , -OCF 3 and/or -C 2 H 5 . Especially preferred are the following patterns: -Phe-Phe.2CH 3 -Phe- -Phe-Phe.2CN-Phe- -Phe-Phe.2CF 3 -Phe- -Phe-Phe.2OCF 3 -Phe- -Phe-Phe.2OCH 3 -Phe- -Phe-Phe.2C 2 H 5 -Phe- -Phe-Phe.2CH 3 3F-Phe- -Phe-Phe.2F3CF 3 -Phe- -Phe-Phe.3CH 3 -Phe- -Phe-Phe.3CN-Phe- -Phe-Phe.3CF 3 -Phe- -Phe-Phe.3OCF 3 -Phe- -Phe-Phe.3OCH 3 -Phe- -Phe-Phe.3C 2 H 5 -Phe- -Phe.3F-Phe.3CH 3 -Phe- -Phe.3Cl-Phe.3CH 3 -Phe- -Phe-Phe.2CH 3 -Phe.3Cl- -Phe-Phe.3CH 3 -Phe.3Cl- -Phe-Phe.2CH 3 -Phe.2Cl- -Phe-Phe.3CH 3 -Phe.2Cl- -Phe-Phe.2Cl-Phe.3CN- -Phe-Phe.3Cl-Phe.3CN- -Phe-Phe.2Cl-Phe.2CN- -Phe-Phe.3Cl-Phe.2CN- -Phe-Phe.2CH 3 -Phe.3CN- -Phe-Phe.3CH 3 -Phe.3CN- -Phe-Phe.2CH 3 -Phe.2CN- -Phe-Phe.3CH 3 -Phe.2CN- -Phe-Phe.3F-Phe.3CN- -Phe-Phe.2F-Phe.3 CN- -Phe-Phe.3F-Phe.2CN- -Phe-Phe.2F-Phe.2CN- -Phe-Phe.2CH 3 -C 2 H 4 -Phe- -Phe-Phe.2Cl-C 2 H 4 -Phe- -Phe-Phe.2CN-C 2 H 4 -Phe- -Phe-Phe.2CHF 2 -C 2 H 4 -Phe- -Phe-Phe.2OCH 3 -C 2 H 4 -Phe- -Phe-Phe.2CF 3 -C 2 H 4 -Phe- -Phe-Phe.2OCF 3 -C 2 H 4 -Phe- -Phe-Phe.2C 2 H 5 -C 2 H 4 -Phe- -Phe-Phe.2CH 3 3F-C 2 H 4 -Phe- -Phe-Phe.2F3CF 3 -C 2 H 4 -Phe- -Phe-C 2 H 4 -Phe.2CH 3 -C 2 H 4 -Phe- -Phe-C 2 H 4 -Phe.2CN-C 2 H 4 -Phe- -Phe-C 2 H 4 -Phe.2OCH 3 -C 2 H 4 -Phe- -Phe-C 2 H 4 -Phe.2CF 3 -C 2 H 4 -Phe- -Phe-C 2 H 4 -Phe.2OCF 3 -C 2 H 4 -Phe- It was observed that the stability of 3-ring compounds wherein one of the 2 groups Z 1 is -COO- or -OCO- while the other denotes a single bond, can be increased if the compound is laterally di- or higher substituted, particularly di-substituted by -Cl, -F, -CN and/or -CH 3 . In the compounds of formula I R 1 is CH 2 = CW 1 -COO-, CH 2 = CH-, HW 1 N-, HS-CH 2 -(CH 2 ) m -COO- with W 1 being H, Cl or alkyl with 1-5 C atoms and m being 1-7. Preferably, R 1 is a vinyl group, an acrylate group, an epoxy group, an amino group or a mercapto group, and especially preferred are the following means of R 1 : CH 2 =CH-COO- R 1 -1 CH 2 =CH- R 1 -4 H 2 N- R 1 -5 H(alkyl)N- R 1 -6 HS-CH 2 -(CH 2 ) m -COO- R 1 -7 with alkyl denoting C 1 -C 3 -alkyl and m being 1-5. In the compounds of formula I, the spacer-type group P is alkylene with up to 12 C atoms, it also being possible for one or more non adjacent CH 2 groups to be replaced by O. In case P is alkylene, P may be straight-chain or branched. P especially preferred is ethylene, propylene, butylene, 1-methyl-propylene, 2-methyl-propylene, pentylene, 1-methyl-butylene, 2-methyl-butylene, hexylene, 2-ethyl-butylene, 1,3-dimethyl-butylene, heptylene, 1-methythexylene, 2-methylhexylene, 3-methylhexylene, 4-methylhexylene, 5-methylhexylene, 6-methylhexylene, octylene, 3-ethyl-hexylene, nonylene, 1-methyloctylene, 2-methyloctylene, 7-methyloctylene, decylene, undecylene, 2-methylundecylene, 2,7,5-trimethyl-nonylene or 3-propyl-nonylene. In case P is mono- or polyoxaalkylene, P may be straightchain or branched. In particular, P is 1-oxa-ethylene, 1-oxa-propylene, 2-oxapropylene, 1-oxabutylene, 2-oxabutylene, 1,3-dioxabutylene, 1-oxa-pentylene, 2-oxapentylene, 3-oxy-pentylene, 2-oxa-3-methyl-butylene, 1-oxahexylene, 2-oxa-hexylene, 3-oxa-hexylene, 1,3-dioxa-hexylene, 1,4-dioxa-hexylene, 1,5-dioxa-hexylene, 1-oxa-heptylene, 2-oxa-heptylene, 1,3-dioxa-heptylene, 1,4-dioxa-heptylene, 1,5-dioxa-heptylene, 1,6-dioxa-heptylene, 1,3,5-trioxa-heptylene, 1-oxa-octylene, 2-oxa-octylene, 3-oxa-octylene, 4-oxa-octylene, 1,3-dioxaoctylene, 1,4-dioxa-nonylene, 1,4-dioxa-decylene, 1,4-dioxa-undecylene and 1,3,5-trioxa-dodecylene. X is -O-, -S-, -COO-, -OCO- or a single bond and in particular -O-, -COO-, -OCO- or a single bond. In case X is -O-, -S- or -COO-, the adjacent CH 2 -group of Q is not replaced by -O-. Z 1 is independently from each other -CH 2 CH 2 - or a single bond. R 2 can be an alkyl radical with up to 15 C atoms which is unsubstituted, mono- or polysubstituted by halogen, it also being possible for one or more CH 2 groups in these radicals to be replaced, in each case independently from one another, by -O-, -S-, -CO-, -OCO-, -COO- or -O-COO- in such a manner that oxygen atoms are not linked directly to one another. If R 2 is an alkyl radical or alkoxy radical, it may be straight-chain or branched. Preferably, it is straight-chain, has 2, 3, 4, 5, 6, 7 or 8 carbon atoms and accordingly is preferably ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy or octoxy, and furthermore methyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy or tetradecoxy. If R 2 is oxaalkyl, it is preferably straight-chain 2-oxapropyl (= methoxymethyl), 2-oxabutyl (= ethoxymethyl) or 3-oxabutyl (= 2-methoxyethyl), 2-, 3- or 4-oxapentyl, 2-, 3-, 4- or 5-oxahexyl, 2-, 3-, 4-, 5- or 6-oxaheptyl, 2-, 3-, 4-, 5-, 6- or 7-oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-oxadecyl. Preferred branched radicals R 2 are isopropyl, 2-butyl (= 1-methylpropyl), isobutyl (= 2-methylpropyl), 2-methylbutyl, isopentyl, (= 3-methylbutyl), 2-methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2-propylpentyl, 2-octyl, isopropoxy, 2-methylpropoxy, 2-methylbutoxy, 3-methylbutoxy, 2-methyl-pentoxy, 3-methyl-pentoxy, 2-ethylhexoxy, 1-methylhexoxy, 2-octyloxy, 2-oxa-3-methylbutyl, 3-oxa-4-methylpentyl, 4-methylhexyl, 2-nonyl, 2-decyl, 2-dodecyl, 6-methyloctoxy, 6-methyloctanoyloxy, 5-methylheptyloxycarbonyl, 2-methylbutyryloxy, 3-methylvaleryloxy, 4-methylhexanoyloxy, 2-chloropropionyloxy, 2-chloro-3-methylbutyryloxy, 2-chloro-4-methylvaleryloxy, 2-chloro-3-methylvaleryloxy, 2-methyl-3-oxypentyl, 2-methyl-3 -oxahexyl. R 2 can also be a polar terminal group and in particular -CN, -Cl or F; R 2 can also be -(L)-C d H e F 2d+1-e wherein L is a single bond, -O- or -S-, d is 1 or 2 and e is 0, 1, 2, 3, 4 or 5. R 2 can also have one of the meanings given for R 1 -Q-X- above. In case R 2 is an - optionally substituted - alkyl radical, R 1 preferable is a vinyl or acrylate group while in case R 2 is R 1 -Q-X, all meanings given above for R 1 are preferred. Reactive liquid crystalline compounds exhibiting two reactive groups R 1 which can be chosen independently from each other, are preferred; especially preferred are compounds exhibiting two identical reactive groups. The reactive liquid crystalline compounds according to formula I and according to the preferred subclasses can be prepared by methods which are known per se and which are described, for example, in standard works of organic chemistry such as, for example, Houben-Weyl, Methoden der Organischen Chemie, Thieme-Verlag, Stuttgart. Some specific methods can be taken from the examples. Methods to introduce the reactive group R 1 as a substituent are well-known in literature. A preferred method to introduce an acrylate group as a terminal substituent into a rod-like molecule is described in examples 1-3. Terminal vinyl ether groups can be introduced, for example, by transetherification reactions. The alcohols are treated with butylvinyl ether in dichloromethane in the presence of 1,10-phenanthroline palladium (II) diacetate as is described in V. Perec, M. Lee and H. Jonsson, J. Polym. Sci. Part A, 1991, 29, 327-337. A thiol group can be introduced, for example, by converting an aliphatic alcohol into a thiol; see, for example, Lucien and Nouveau, J. Chem., 1979, 3 , 15. The "ene" group can be introduced by directly alkylating the core with a suitable ω-bromo-α-alkene. The reaction methods mentioned are briefly summarized in the following synthetic tree: The reaction schemes mentioned above are to illustrate the invention without restricting it. The expert can choose other reaction methods without any inventive efforts. In the following and in the preceding, all percentages given are percentages by weight. Temperatures are given in degrees Celsius. The following examples are intended to illustrate the invention without restricting it. Example 1 The reactive liquid crystalline compound (1) is prepared via the sequence of reaction steps shown in diagram 1. Compound (1) exhibits the following phase sequence: n=3: K 73 N 80 I n = 6: K 69 S A 75 N 78.6 I Example 2 The reactive liquid crystalline compound (2) is prepared via the sequence of reaction steps shown in diagram 2. Example 5 The reactive liquid crystalline compound (5) is prepared by reacting the compound obtained in step 3 of diagram 1 according to diagram 4. Compound (5) exhibits the following phase sequence. n = 3: K 74.4 (S 37.7 N 52.6) I n = 6: K 79.4 S 89.6 N 111.4 I

Claims: Reactive liquid crystal compound of formula I R 1 -P-X-(A 1 -Z 1 ) n -A 2 -R 2 wherein R 1 is CH 2 =CW 1 -COO-, CH 2 =CH-, HW 1 N- or HS-CH 2 -(CH 2 ) m -COO-, with W 1 being H, Cl or alkyl with 1-5 C-atoms and m being 1-7, P is alkylene with up to 12 C atoms, it being also possible for one or more CH 2 groups to be replaced by O in such a manner that oxygen atoms are not directly linked to one another, X is -O-, -S-, -COO-, -OCO- or a single bond, R 2 is an alkyl radical with up to 15 C atoms which is unsubstituted, mono- or polysubstituted by halogen, it being also possible for one or more CH 2 groups in these radicals to be replaced, in each case independently of one another, by -O-, -S-, -CO-, -O-CO-, -CO-O- or -O-CO-O- in such a manner that oxygen atoms are not linked directly to one another, or alternatively R 2 has one of the meanings given for R 1 -P-X or is CN, F, Cl or -V-Q-T wherein V is -O-, -S- or a single bond, Q is -CH 2 -, CHF-, -CF 2 -, and T is F or Cl, n is 1 or 2, A 1 , A 2 are independently from each other 1,4-phenylene which is unsubstituted or mono- or polysubstituted by F, Cl, CN or -W 2 -C r H s F 2r+1-s , and one of A 1 and A 2 may also denote pyridine-2,5-diyl or pyrimidine-2,5-diyl, Z 1 is independently from each other -CH 2 -CH 2 - or a single bond, in case n=2 both the moieties A 1 as well as both the moieties Z 1 are having the meaning given above, independently from each other, r is 1 or 2, s is 0, 1, 2, 3, 4 or 5, W 2 is a single bond, -O-, -S- or -CO-, with the provisos (i) that at least one of A 1 and A 2 is 1,4-phenylene which is mono- or polysubstituted by Cl, CN or -W 2 -C r H s F 2r+1-s , it also being possible for this substituted 1,4-phenylene group to be additionally substituted by one or more F-atoms, and (ii) that in case n=2 at least one of A 1 and A 2 is double substituted or at least two of A 1 and A 2 are substituted, characterized in that said compound is laterally di- or higher substituted by CN or -W 2 -C r H s F 2r+1-s . Reactive liquid crystal compound according to claim 1, characterized in that -A 1 -Z 1 -A 1 -Z 1 -A 2 - is wherein L 1 and L 2 are independently from each other -CN or-W 2 -C r H s F 2r+1-s , and W 2 , r and s have the meanings of claim 1. Reactive liquid crystal compound according to claim 1 or 2, characterized in that it is laterally di- or higher substituted by -CN, -CH 3 , -OCH 3 , -CF 3 or -OCF 3 . Reactive liquid crystal compound of formula I2 R 1 -P-X-A 1 -Z 1 -A 2 -R 2 wherein R 1 is CH 2 =CW 1 -COO-, CH 2 =CH-, HW 1 N- or HS-CH 2 -(CH 2 ) m -COO-, with W being H, Cl or alkyl with 1-5 C-atoms and m being 1-7, P is alkylene with up to 12 C atoms, it being also possible for one or more CH 2 groups to be replaced by O in such a manner that oxygen atoms are not directly linked to one another, X is -O-, -S-, -COO-, -OCO- or a single bond, R 2 is an alkyl radical with up to 15 C atoms which is unsubstituted, mono- or polysubstituted by halogen, it being also possible for one or more CH 2 groups in these radicals to be replaced, in each case independently of one another, by -O-, -S-, -CO-, -O-CO-, -CO-O- or -O-CO-O- in such a manner that oxygen atoms are not linked directly to one another, or alternatively R 2 has one of the meanings given for R 1 -P-X or is CN, F, Cl or -V-Q-T wherein V is -O-, -S- or a single bond, Q is -CH 2 -, -CHF-, -CF 2 -, and T is F or Cl, A 1 , A 2 are independently from each other 1,4-phenylene which is unsubstituted or mono- or polysubstituted by F, Cl, CN or -W 2 -C r H s F 2r+1-s , and one of A 1 and A 2 may also denote pyridine-2,5-diyl or pyrimidine-2,5-diyl, Z 1 is independently from each other -CH 2 -CH 2 - or a single bond, r is 1 or 2, s is 0, 1, 2, 3, 4 or 5, W 2 is a single bond, -O-, -S- or -CO-, with the proviso that at least one of A 1 and A 2 is 1,4-phenylene which is monosubstituted by Cl, CN or -W 2 -C r H s F 2r+1-s , it also being possible for this substituted 1,4-phenylene group to be additionally substituted by one or more F-atoms, characterized in that said compound is laterally monosubstituted by -Cl, -CN or -W 2 -C r H s F 2r+1-s . Reactive liquid crystal compound of formula I3 R 1 -P-X-A 1 -Z 1 -A 1 -Z 1 -A 2 -R 2 wherein R 1 is CH 2 =CW 1 -COO-, CH 2 =CH-, HW 1 N- or HS-CH 2 -(CH 2 ) m -COO-, with W 1 being H, Cl or alkyl with 1-5 C-atoms and m being 1-7, P is alkylene with up to 12 C atoms, it being also possible for one or more CH 2 groups to be replaced by O in such a manner that oxygen atoms are not directly linked to one another, X is -O-, -S-, -COO-, -OCO- or a single bond, R 2 is an alkyl radical with up to 15 C atoms which is unsubstituted, mono- or polysubstituted by halogen, it being also possible for one or more CH 2 groups in these radicals to be replaced, in each case independently of one another, by -O-, -S-, -CO-, -O-CO-, -CO-O- or -O-CO-O- in such a manner that oxygen atoms are not linked directly to one another, or alternatively R 2 has one of the meanings given for R 1 -P-X or is CN, F, Cl or -V-Q-T wherein V is -O-, -S- or a single bond, Q is -CH 2 -, -CHF-, -CF 2 -, and T is F or Cl, A 1 , A 2 are independently from each other 1,4-phenylene which is unsubstituted or mono- or polysubstituted by F, Cl, CN or -W 2 -C r H s F 2r+1-s , and one of A 1 and A 2 may also denote pyridine-2,5-diyl or pyrimidine-2,5-diyl, Z 1 is independently from each other -CH 2 -CH 2 - or a single bond, in case n=2 both the moieties A 1 as well as both the moieties Z 1 are having the meaning given above, independently from each other, r is 1 or 2, s is 0, 1, 2, 3, 4 or 5, W 2 is a single bond, -O-, -S- or -CO-, with the proviso that at least one of A 1 and A 2 is 1,4-phenylene which is mono- or polysubstituted by Cl, CN or -W 2 -C r H s F 2r+1-s , it also being possible for this substituted 1,4-phenylene group to be additionally substituted by one or more F-atoms, characterized in that said compound is laterally monosubstituted by Cl, -CN or -W 2 -C r H s F 2r+1-s . with the proviso that compounds being only monosubstituted by Cl are excluded. Reactive liquid crystal compound according to claim 5, characterized in that -A 1 -Z 1 -A 1 -Z 1 -A 2 - is wherein L 1 and L 2 are independently from each other -F, -Cl,-CN or -W 2 -C r H s F 2r+1-s , and W 2 , r and s have the meanings of claim 1. Reactive liquid crystal compound according to claim 4, 5 or 6, characterized in that it is laterally monosubstituted by -CH 3 , -O-CH 3 , -CF 3 , -OCF 3 , -CH 2 F, OCH 2 F, -OHF 2 , -OCHF 2 , -C 2 H 5 , -S-CH 3 or -S-CF 3 . Reactive liquid crystal compound according to any of claims 1 to 7, characterized in that R 2 has one of the meanings of R 1 -P-X-in formula I. Reactive liquid crystal compound according to any of claims 1 to 8, characterized in that R 1 is vinyl or acrylate. Use of liquid crystal materials according to any of claims 1 to 8 in electrooptical scattering systems or for the preparation of oriented liquid crystal polymers.

Inventors: BONNY IAN, COATES DAVID DR, GREENFIELD SIMON DR, PARRI OWAIN LLYR DR, BONNY, IAN, COATES, DAVID, DR., GREENFIELD, SIMON, DR., PARRI, OWAIN LLYR, DR.
Applicants: MERCK PATENT GMBH
Application year: 1994
Main classification: C09K19
IPC codes: C09K19, C07C69